Solvent-dependent chemoselective synthesis of different isoquinolinones mediated by the hypervalent iodine(III) reagent PISA.

Isoquinolinone is an important heterocyclic framework in natural products and biologically active molecules, and the efficient synthesis of this structural motif has received much attention in recent years. Herein, we report a (phenyliodonio)sulfamate (PISA)-mediated, solvent-dependent synthesis of different isoquinolinone derivatives. The method provides highly chemoselective access to 3- or 4-substituted isoquinolinone derivatives by reacting o-alkenylbenzamide derivatives with PISA in either acetonitrile or wet hexafluoro-2-isopropanol.

A review: analysis of technical challenges in cultured meat production and its commercialization.

The cultured meat technology has developed rapidly in recent years, but there are still many technical challenges that hinder the large-scale production and commercialization of cultured meat. Firstly, it is necessary to lay the foundation for cultured meat production by obtaining seed cells and maintaining stable cell functions. Next, technologies such as bioreactors are used to expand the scale of cell culture, and three-dimensional culture technologies such as scaffold culture or 3D printing are used to construct the three-dimensional structure of cultured meat. At the same time, it can reduce production costs by developing serum-free medium suitable for cultured meat. Finally, the edible quality of cultured meat is improved by evaluating food safety and sensory flavor, and combining ethical and consumer acceptability issues. Therefore, this review fully demonstrates the current development status and existing technical challenges of the cultured meat production technology with regard to the key points described above, in order to provide research ideas for the industrial production of cultured meat.

The Effect of Long-Term Passage on Porcine SMCs' Function and the Improvement of TGF-ß1 on Porcine SMCs' Secretory Function in Late Passage.

Cultured meat is one of the meat substitutes produced through tissue engineering and other technologies. Large-scale cell culture is the key for cultured meat products to enter the market. Therefore, this study is aimed to explore the effect of long-term passage in vitro on smooth muscle cells (SMCs) and the effect of transforming growth factor-ß1 (TGF-ß1) on SMCs in the late passage. Multiple passages lead to the decline of the proliferation rate of SMCs in the proliferation stage and the differentiation ability in the differentiation stage. Transcriptome results showed that the ECM pathway and aging-related signaling pathways were significantly up-regulated in the late passage period. TGF-ß1 did not promote SMCs of late passage proliferation at the proliferation stage but promoted the gene and protein expression of collagen as the main protein of the extracellular matrix proteins at the differentiation stage. In addition, proteomic analysis revealed that TGF-ß1 promoted the expression of cell adhesion molecules which activate the Hippo signaling pathway and the HIF-1 signaling pathway and further promoted the production of collagen-containing extracellular matrix proteins. This could provide ideas for large-scale production of cultured meat products using SMCs.

A semi-encapsulated PdRh alloy heterojunction for the selective catalytic hydrogenation of nitrophenylacetylene to nitrostyrene.

Semi-hydrogenation usually requires an effective catalyst to ensure selectivity, especially when reducible groups coexist in a molecule. Pd is widely used in the semi-hydrogenation of alkynes to synthesize alkenes, but the selectivity control is still challenging. Herein, we design a catalyst with a semi-encapsulated PdRh alloy heterojunction in a carbon layer for the selective semi-hydrogenation of 3-nitrophenylacetylene (3-NPA). Benefiting from the presence of a PdRh alloy heterojunction and a semi-encapsulated structure, the catalyst delivers good selectivity and maintains high activity. In addition, the carbon shell can ensure the stability of the catalyst and prolong the service life. This study provides ideas for the rational design of a catalyst to achieve a selective hydrogenation reaction for practical applications.

Iron Catalyzed Cascade Construction of Molybdenum Carbide Heterointerfaces for Understanding Hydrogen Evolution.

The intercrystalline interfaces have been proven vital in heterostructure catalysts. However, it is still challenging to generate specified heterointerfaces and to make clear the mechanism of a reaction on the interface. Herein, this work proposes a strategy of Fe-catalyzed cascade formation of heterointerfaces for comprehending the hydrogen evolution reaction (HER). In the pure solid-phase reaction system, Fe catalyzes the in situ conversion of MoO2 to MoC and then Mo2 C, and the consecutive formation leaves lavish intercrystalline interfaces of MoO2 -MoC (in Fe-MoO2 /MoC@NC) or MoC-Mo2 C (in Fe-MoC/ß-Mo2 C@NC), which contribute to HER activity. The improved HER activity on the interface leads to further checking of the mechanism with density functional theory calculation. The computation results reveal that the electroreduction (Volmer step) produced H* prefers to be adsorbed on Mo2 C; then two pathways are proposed for the HER on the interface of MoC-Mo2 C, including the single-molecular adsorption pathway (Rideal mechanism) and the bimolecular adsorption pathway (Langmuir-Hinshelwood mechanism). The calculation results further show that the former is favorable, and the reaction on the MoC-Mo2 C heterointerface significantly lowers the energy barriers of the rate-determining steps.

Encapsulating Electron-Rich Pd NPs with Lewis Acidic MOF: Reconciling the Electron-Preference Conflict of the Catalyst for Cascade Condensation via Nitro Reduction.

Cascade reactions take advantage of step-saving and facile operation for obtaining chemicals. Herein, catalytic hydrogenation of nitroarene coupled condensation with ß-diketone to afford ß-ketoenamines is achieved by an integrated nanocatalyst, Pd-e@UiO-66. The catalyst has the structure of an acid-rich metal-organic framework (MOF), UiO-66-encapsulated electron-rich Pd nanoparticles, and it reconciles the electron-effect contradiction of cascade catalytic reactions: catalytic hydrogenation requires an electron-rich catalyst, while condensation requires electron-deficient Lewis acid sites. The catalyst showed good activity, high chemoselectivity, and universal applicability for the synthesis of ß-ketoenamines using nitroarenes. More than 30 ß-ketoenamines have been successfully prepared with up to 99% yield via the methodology of relay catalysis. The catalyst exhibited excellent stability to maintain its catalytic performance for more than five cycles. Furthermore, we conducted an in-depth exploration of the reaction mechanism with theoretical calculations.

Singlet Oxygen Generation from a Water-Soluble Hypervalent Iodine(V) Reagent AIBX and H2O2: An Access to Artemisinin.

Herein, we report an efficient method for the chemical generation of 1O2 by treatment of H2O2 with AIBX, a highly water-soluble, bench-stable, recyclable hypervalent iodine(V) reagent developed by our group. The generation of 1O2 was confirmed by the following results: (1) capture of 1O2 with the sodium salt of anthracene-9,10-bis(ethanesulfonate) produced the corresponding endoperoxide and (2) TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) produced by the oxidation of 2,2,6,6-tetramethylpiperidine with 1O2 generated using the AIBX/H2O2 system was detected by electron spin resonance spectroscopy. To illustrate the potential utility of this method for organic synthesis, we used the AIBX/H2O2 system to perform typical reactions of 1O2: [2 + 2]/[4 + 2] cycloadditions, Schenck ene reactions, and heteroatom oxidation reactions, which afforded the corresponding products in high yields. Moreover, we used the method to synthesize the antimalarial drug artemisinin. Finally, we demonstrated that AIBX could be regenerated after the reaction by means of a workup involving extraction and removal of water to obtain a precursor of AIBX, which could then be re-oxidized.

Ring Expansion Fluorination of Unactivated Cyclopropanes Mediated by a New Monofluoroiodane(III) Reagent.

Herein, we report a new strategy for carbon-carbon bond scission and intramolecular ring expansion fluorination of unactivated cyclopropanes, which was accomplished with a new hypervalent fluoroiodane(III) reagent 1. This novel method delivers medicinally relevant 4-fully substituted fluoropiperidines in moderate to high yields with excellent regio- and diastereoselectivity. Reagent 1, which has an N-acetylbenziodazole framework, was readily synthesized via three steps in 76 % overall yield and was characterized by NMR spectroscopy and X-ray crystallography. Owing to the presence of a secondary I⋅⋅⋅O bonding interaction between the λ3 -iodane atom and the carbonyl oxygen of the acetyl group of the N-acetylbenziodazole framework, 1 has excellent stability and can be stored at ambient temperature for 6 months without any detectable decomposition. Density functional theory calculations and experimental studies showed that the reaction proceeds via a carbocation intermediate that readily combines with a fluoride ion to generate the product.

Metal-Organic Framework-Encapsulated CoCu Nanoparticles for the Selective Transfer Hydrogenation of Nitrobenzaldehydes: Engineering Active Armor by the Half-Way Injection Method.

A novel armor-type composite of metal-organic framework (MOF)-encapsulated CoCu nanoparticles with a Fe3 O4 core (Fe3 O4 @SiO2 -NH2 -CoCu@UiO-66) has been designed and synthesized by the half-way injection method, which successfully serves as an efficient and recyclable catalyst for the selective transfer hydrogenation. In this half-way injection approach, the pre-synthetic Fe3 O4 @SiO2 -NH2 -CoCu was injected into the UiO-66 precursor solution halfway through the MOF budding period. The formed MOF armor could play a role of providing significant additional catalytic sites besides CoCu nanoparticles, protecting CoCu nanoparticles, and improving the catalyst stability, thus facilitating the selective transfer hydrogenation of nitrobenzaldehydes into corresponding nitrobenzyl alcohols in high selectivity (99 %) and conversion (99 %) rather than nitro group reduction products. Notably, this method achieves the precise assembly of a MOF-encapsulated composite, and the ingenious combination of MOF and nanoparticles exhibits excellent catalytic performance in the selective hydrogen transfer reaction, implementing a "1+1>2" strategy in catalysis.

Selective Synthesis of Symmetrical Secondary Amines from Nitriles with a Pt-CuFe/Fe3 O4 Catalyst and Ammonia Borane as Hydrogen Donor.

Hydrogenation of nitriles is an efficient and environmentally friendly route to synthesize symmetrical secondary amines, but it usually produces a mixture of amines, imines, and hydrogenolysis by-products. Herein we report a magnetic quaternary-component Pt-CuFe/Fe3 O4 nanocatalyst system for the selective synthesis of symmetrical secondary amines with ammonia borane as hydrogen donor. The catalyst with a low Pt loading (0.456 wt%) is the source of the activity, and the d-band electron transfer from Cu to Fe enhances the selectivity. This synergistic effect results in the transformation of benzonitrile to dibenzylamine with excellent conversion (up to 99 %) and nearly quantitative selectivity (up to 96 %) under mild reaction conditions, nevertheless, the reaction TOF is as high as up to 1409.9 h-1 . A variety of nitriles are suitable for the synthesis of symmetrical secondary amines. More importantly, unwanted hydrogenolysis byproducts, especially toluene, is not detected at all. In addition, the catalyst is magnetically recoverable, and it can be reused up to five times.

Cobalt-promoted fabrication of 3D carbon with a nanotube-sheet mutual support structure: scalable preparation of a high-performance anode material for Li-ion batteries.

Currently, the design of carbon-based composite as a high-performance anode material for lithium-ion batteries (LIBs) presents challenges for commercial application. Herein, we developed a three-dimensional carbon-based material with a nanotube-sheet mutual support structure (MS-CNTS) engineered by the catalytic effect of Co species. The present work highlights a concise 'solvent-free' synthetic method allowing for large-scale output, which is potentially available for low cost commercial use. With the readily available acetylacetonate and cobalt (II) acetylacetonate as starting chemicals, this nanostructured carbonaceous material is fabricated with aldol condensation to construct a Co-contained carbon-link network polymer precursor followed by annealing under argon. It is composed of brim-curled graphene-like carbon nanosheets and carbon nanotubes, which support each other's structures to effectively avoid agglomeration. Therefore, it enables high performance in LIBs. In spite of the trace amount of cobalt, the carbon-based MS-CNTS anode delivers a high charge capacity of 1028 mAh g-1 at 0.1 A g-1, high rate capacity of 495 mAh g-1 at 2 A g-1, and ultra-long cycling life with a very low capacity decay of 0.008% per cycle over 1000 cycles at 0.5 A g-1, accompanied by 100% Coulombic efficiency. From full cell measurements, we further confirm the considerable promise of MS-CNTS as anodes with a long cycling life.

Interaction between cyclooxygenase-2, Snail, and E-cadherin in gastric cancer cells.

AIM: To investigate the mechanisms of how cyclooxygenase-2 (COX-2) regulates E-cadherin in gastric cancer cells. METHODS: COX-2 expression in human gastric cancer cell lines SGC-7901, BGC-823, MGC-803 and AGS were measured at the mRNA and protein level. COX-2 rich cell line SGC-7901 was chosen for subsequent experiments. siRNA mediated gene knockdown was used to investigate the impact of COX-2 on nuclear factor-κB (NF-κB), Snail, and E-cadherin in gastric cancer cells. Gene expression was determined by Western blot and real-time polymerase chain reaction. To analyze whether NF-κB inhibition could interrupt the modulatory effect of COX-2 or prostaglandin E2 (PGE2) on E-cadherin, gastric cancer cells were treated with celecoxib or PGE2, in the presence of NF-κB specific siRNA. RESULTS: Highest expression level of COX-2 was found in SGC-7901 cells, both at mRNA and protein levels. siRNA mediated down-regulation of COX-2 led to a reduced expression of NF-κB and Snail, but an increased expression of E-cadherin in SGC-7901 cells. siRNA mediated down-regulation of NF-κB also led to a reduced expression of E-cadherin and Snail in SGC-7901 cells. However, COX-2 expression did not alter after cells were treated with NF-κB specific siRNA in SGC-7901 cells. Treatment of SGC-7901 cells with celecoxib led to a reduced expression of Snail but an increased expression of E-cadherin. In contrast, treatment of SGC-7901 cells with PGE2 led to an increased Snail and a decreased E-cadherin. However, siRNA-mediated knockdown of NF-κB partially abolished the effect of celecoxib and PGE2 on the regulation of E-cadherin and Snail in SGC-7901 cells. CONCLUSION: COX-2 likely functions upstream of NF-κB and regulates the expression of E-cadherin via NF-κB/Snail signaling pathway in gastric cancer cells.